Process for refining oils and waxes



July 24, 1928. 1,678,298

`. W. A. PATRICK ET AL PROCESS FOR REFINING OILS AND wAXEs Filed March 16, 1922 3 sheets-sheet, 1

July 24, i928. 4 1,678,298

W. A. PATRICK ET AL PRcEss FOR REFINING oILs AND wAXEs Filed March 16, 1922 :5 sheets-sheet 2 July 24, '1928.

W. A? PATRICK ET AL PROCESS FOR REFINING OILS AND WAXES Filed March 16. 1922 form of agitator that may be Patented July 24, 1928.

WALTER ALBERT PATRICK,

OF BALTIMORE, MARYLAND,

BALTIMORE or MOUNT WASHINGTON, AND

NT OFFICE.

ERNEST BALDWIN MILLER,

ASSIGNORS TO THE' SILICA GEL CORPORATION, OI"

, MARYLAND, A CORPORATION 0F MARYLAND.

PROCESS lFOR REFINING OILS AND WAXES.

Application filed March 16,1922. serial No. 544,186.

The present invention relates to a process for `refining oils A prior appl Patrick discloses the discovery that porous and waxes. ication Patent '1,537,260 to bodies having ultra-microscopic pores. will adsorb certain conditions.

'certain solutes from solution under The present invention is in the nature of a species under the broad invention covere d by said patent. Accord- 'ing to the present invention, it has been discovered that oils can ing, with porous bodies,

be refined by adsorbimpurities that are inl solution in the oils, providedthe adsorbing material has ward the substance to Ward the oils.

Briefly stated,

sists in adsorbing the impurities from thel pores of 'an adsorbing material ultra-microscopic pores, then liberoil in the having a lower surface tension tobe adsorbed thanl tothe present invention con ating the substance adsorbed in the material and using ining more oil.

For purposes tion the rening of gasoline or kero understood, how

plies to waxes andoils in animal and m the material again for reof illustration, the invenwill be described in connection with petroleum products, such as sene. ever,

It is to be distinctly that the invention apgeneral, vegetable, including benzine,

ineral,

toluene, carbon-tetrachloride and aniline.

The objects'and features ofnovelty of the invention Wi scription taken in ings, in which ll be apparent from the deconnection with the draw- Figure 1 is a diagrammatic view illustrating in elevation one` form of apparatus for refining such liquids as petroleum prod-` ucts;

Figure 2 is asectional elevation of one the apparatus;

Figure 3 is a employed in sectional elevation of. one

form of separator that may be used in the apparatus;

Figure 4 is asectiona'l plan view 'taken substantially the line 4 4 of Figure 1,

showing a feed device; and

Figure 5 is a longitudinal sectional elevation through one form of activator that may be employed.l

In said prior closed that a so atent, the discovery is dis- 'fill the .pores in silica gel a partial pressure of yof mercury. Kieselguhr and boneblack uIider the above conditions will adsorb practi.

a solution under certain conditions of a porous material having very i'ine or ultra-microscopic pores. The pores of the adsorbing material required are so small that it is a very diilcult matter to accurately determinel and define their size. For this purpose, however, reference may be had to the amount of water that one gram of material will adsorb when exposed to water vapor under denite condition of temperature and partial pressure of Water vapor.

A liquid that wets capillary tube will rise in the tube above the level ofthe surface of the li uid surrounding thesaine, the extent of t e rise varying withI the diameter of the tirhe. The vapor pressure of the liquid inside the tube is smaller thanthe vapor pressure at the level surface of the liquid outside the tube. This lowering of the vapor pressure by the liquid within the capillary'tube is not appreciable until the diameter of the tube is extremely small, and the smaller decrease in vapor pressure. The amount of water adsorbed by a porous body at a given temperature and partial pressure depends both upon the size ot the pores and upon the total interior volume of the pores. By determining the amount of a given material, water for example, Which may be adsorbed by each of the porous bodies under the same condition of temperature and partial pressure, we have a means of comparing the size andvolume of the pores in the two adsorbents. For example, one gram of silica gel (made in accordance if we completely with Water,` the amount of water taken up Will be approximately 41% of the initial weight of the gel. A suHicient percentage of the total internal volume in silica gel is made up of pores of such size that the gel will adsorb water vapor to such an extent as to contain at least 21% of itsown weight lof Water when in equilibrium with water vapor at 30o C.' and substantially 22 mm.

0.41 cc. In other words,

cally no water. Highly activated charcoal, suoli as cocoanut charcoal, will adsorb more water than the silica gel mentioned above the bore of the tube, the greater the l with .Patent 1,297',-` 724) has a total internal volume of about by means provided it is wetted byv water. It follows,

therefore, that kieselguhr and boneblack have practically no pores as small as the greater part of the pores in silica gel. On the other hand, highly activated charcoal has more small pores than silica gel.

It has been found that materials which adsorb water vapor to such an extent as to contain less than 10% of their initial weight of water when in equilibrium with water vapor at 300 C. and a partial pressure of substantially 22 min. of mercury have pores too large to be of any practical valuein adsorbing solutes from solutions.

The material preferred for practicing said prior and the present method is silica gel having a structure like that obtained when the gel is made in accordance the method disclosed'in the patent to Patrick 1,297,724. In cases where silica gel is not suitable, other gels or adsorbing materials may be used. provided they have a sulicient number of small pores as defined above, i. e., activated charcoal, gels of iron oxide, tin oxide, aluminum oxide, tungstic oxide, zirconium oxide, and titanium oxide.

The hard porous silica gel preferably employed as an adsorbing material in the present invention should be distinguished from the dried gelatinous precipitate obtained for example bv mixing an acid and sodium silicate and then drying.' This latter product, however, when dried, does not have the porous structure of the gel made in accordance with said patent or by dialysis, and is not suitable to adsorb solutes from solutions to any practical extent. According to said patent, solutions of an-.acid and a substance are employed of such concentrations and in suoli quantities that t-he substance will react with the acid to form a homogeneous, colloidal solution of silicie acid. Immediate coagulation of the mass is prevented by thorough stirring at the time of mixing the ingredients. Three or four hours after mixing, the substance 'sets without precipitation to a homogeneous, jelly-like mass and, when this is dried slowly in accordance with the method described in the patent, ahard' porous gel is obtained, the pores being ultramicroscopic.

According to said prior invention that solute will be adsorbed from a solution that exhibits the smallest surface tensionl Itoward the wall of the porous material. Furthermore, theseparation of a new phase from the solution is easier the smaller the solubility of'the substance in the solution. As a measure of solubility, the critical solution temperature may be selected. The greatest adsorptive effect will be obtained from a solution having the highest critical solution temperature. Moreover', the extent ,of the adsorption is also 'influenced by the difference in density between the components of the solution. The smaller' the difference in density, the greater will be the adsorption of one of the components from the solution.

Having set fort-h the principal features of said prior invention, the present invention will now be described. Although the present invention is applicable to oils in general, it will be described as applied to reining gasoline or kerosene.

Straight run and cracked gasoline and kerosene distillates in general contain sulphur compounds, have a disagreeable or sour odor and a yellow color. All these features vary widely with diiferent products, depending upon the sourcel of the crude oil, upon whether it is a straight run distillate or a product of cracking.

The exact form in which sulphur exists in gaitoline'or kerosene has been the subject of considerable study and the solution of the problem is still incon'lplete. It is well known that there are at least two forms, one which re-acts to the doctor test and one lwhich does not. This doctor test consists in adding a solution ofl lead oxide and sodium hydroxide to a sample ofthe hydrocarbon. Certain of thesulphur compounds, if present in the sample, will re-act with the solution to color it. In all probability, ordinary unreined gasoline and kerosene contain a varying quantity of complex organic Sulphur conipounds, some of which give 'a positive re-action to the doctor solution. They may contain also some simpler compounds of sulphnr, possibly of different types, which do not re-act with the doctor solution. It is also believed that some gasolines contain dissolved elementary sulphur. It is known that dissolved sulphur may give a negative doctor test. It is further known that certain gasolines and kerosenes containing sulphur and giving a negative doctor test will., after standing, develop a positive doctor test. Such a change is accelerated by heat and light and by Contact with air (oxygen) and. moisture. As a result, we often find that a gasoline or kerosene, refined by chemical treatment to give a negative doctor test, will lateishow a positive re-action toward the doctor solution.

The same is true regarding both color and odor. Thus a gasoline, for example, may be refined by chemical treatment, Such as with sulphuric acid, alkali and lead oxide, to Such an extent that the product is water white or nearly so and has a sweet odor, but on standing this apparently satisfactory product, particularly if exposed to light, moisture and oxygen, will develop a yellow color and a sour odor.

It is thought that the re-appearance of a positive doctor test' is due to chemical changes taking place subsequent to refining, as a result of which sulphur or Sulphur compounds not removed by the process of refining employed are changed into different compounds which givea positive re-action toward the doctor solution. Such changes appear to involve certain unsaturated constituents of the gasoline aswell as sulphur. Thesel same or similar changes give risev also to a sour odor and result in the formation of gummy substances which remain dissolved in the gasoline, imparting a yellow color to it. 'y

Petroleum products, such as gasoline and kerosene, refined in accordance with the present invention, although high in unsaturated constituents, remain colorless or Water White indefinitely, even when exposed to air and light. These refined hydrocarbons, having more than 10% unsaturated hydrocarbons and a sulphur content below 0.02%, which remain indefinitely colorless are new prod.

ucts. The relative amounts of unsaturated hydrocarbons may be determined byre-action with,93% sulphuric acid as described in Bulletin No. 5, Bureau of Mines, December v(Sti 29, 1920. Moreover, no known refined petroleum product having over 10% unsaturated hydrocarbons which will give a negative gum test, has been made.- This test consists in evaporating to dryness 100 cc. of the sample in a polished copper dish. Fora negative' ltest there should be no discoloring of the dish nor deposit left. This test is described in Bulletin No. 5, Bureau of Standards, page V3, Corrosion Test. The product obtained by refining suffieientlyin `accordance with the present invention gives a negative um test. In this respect in addition to the ot ers, the product is new.A

. Briefiystated,'according to the present invention, the petroleum product is refined by bringing the crude product into intimate contact. with an adsorbing material having pores of a size to adsorb the matter in solufion, the material preferabl v.bein r powdered condition; allowing t e liqui and adsorbed material to remain in contact until the objectionable constituents are adsorbed by the material and thereafter separating the refined product from the material. vIt is also desired to liberate the adsorbed impurities from the adsorbing material, such as silica gel, so that the adsorbent may be used over again. Generally, this is laecomplished by driving out the substance adsorbed in tle adsorbing material by immersing the material in a liquid that has a lower surface tension at an interface with the adsorbing material than the substances adsorbed, so that the latter are replaced by the liquid; and then activating the material by driving off or liberating the liquid. For the products having higher boiling points this -wash isnot sufficient and in addition steam activation may be employed.

For the purpose of adsorbing the impurities and matters in solution from the petroleum to be refined, any one of several'methods may vbe used. For example, the crude liquid may be madevto percolate through a tower filled with a porous adsorbing material, such as silica gel, and the refined product drawn off' at the bottom of the tower. After the gel has become saturated with the impurities being removed from .the liquid, the crude is diverted to a second similar tower, while the gel in the first tower is reactivated by suitable means.

In practice, however, it is preferred to use a different method. The preferred method consists in causing a stream of crude liquid to enter at one end of and toflow successively through a series of agitators and separators, containing a proper porous adsorbing material, such as silica gel, Which is fed in continuously at the end opposite to that at which rthe liquid enters and by appropriate means made to move in the direction ,way a part of the ob'ectionable constituents.,

of the liquid being re ned is removed at each stage, as the liquid fiows through the apparatus, until finally the refining is completed in the last stage, where the liquid, which has already had most of the'impurities removed, comes in contact with freshly activated adsorbing material.

Referring to the drawin s,the li uid to be refined, such as a petro eum pro uct, is supplied to a pump 10 by a pipe 11 and thisV pump through the pipe 12 feeds the `petroleum into an agitator'13. This agitator may be of any suitable construction., As shown in Figure 2, it may consist of a closed vessel 14 having a vertical shaftl,A provided With blades 16, said shaft projecting above the to of thevessel and having a pulley 17 w ereby the shaft is rotated.l

vertically in the vessel and adjacent the bottom thereof has the deflectors 21 for forcing the adsorbing material, which settles at the bottom, toward the outlet. Around the top of the vessel may be a launder 22. The adsorbing material settles to the bottom of the tank and is discharged through A the outlet, while the petroleum product fiows into the launder and is carried by a pipe 23 to an agitator 132 and a pump 24 acts to continuously supply adsorbm materiall to said agitator 132. The mixture is discharged from this second agitator eilthrough a pipe 25 to a second separator 202. ln the same manner as previously described, the adsorbing material settles to the bottom of this se arator and the petroleum is discharged t rough a pipe 26 into a third agitator 133. rl`his agitator is supplied with freshly activated adsorbing material from a hopper 27. The mixture from the agitator is conveyed by the pipe 28 to a third separator 203. rlhe reiined petroleum |is discharged from this separator through a pipe 29. The adsorbing material which settles to the bottom or" the third separator is discharged through the outlet in the bottom and conveyed by the pipe 30 to the pump 2d', previously mentioned, this pump. acting to'cause the flow ot the adsorbing material. rlhe adsorbing material discharged at the bottom of the second or middle separator is conveyed by a pipe 31 to a pump` 45 which discharges into the pipe 18 previously mentioned. rlhis pump a5 cilects the flow in the pipe 3l.

Although an apparatus having three units, each unit consisting of an agitator and a separator has been described the invention is not limited to any particular numl ber of units.

llt will be noted that the fresh, orl activated gel is fed into the system to act on the product being rel-ined just before it is iinally discharged and then its path through the apparatus is from the discharge end toward the inlet end. Thus, the product ted into the irst agitator 13 is mixed with adsorbing material that has already passed through a plurality of separators. This counter-How of the adsorbing material and the petroleum to be refined gives a very etilcient action.

The adsorbing material settling in the bottom 0I" the first separator 20 is discharged into a pipe 33. This adsorbing material has adsorbed impurities from the petroleum and, of course, has petroleum associated therewith. ln order to make the process continuous, it is now necessary to free the adsorbing material from its adsorbed substances or activate it.

So far as liquids similar to gasoline, kerosene and benzol are concerned, they may be distilled out of gels without diiiiculty as by steam activation claimed in application 566,664, filed .lune 7, 1922. The objectionable substances removed by the adsorption, however, often consist of or contain compleX organic compounds, usually associa-ted with sulphur, which on heating to a sufiiciently high temperature to volatilize 'them undergo decomposition in the gel, frequently with deposition ot carbonaceous and gummy materials, diiicult to remove from the gel. This difficulty is aggravated in the refining of lubricating oils, waxes, etc.

In all phenomena in connection with adbeen saturated with gasoline, for eXar/nple,

(or other liquid immiscible with water) is brought in Contact with water, the latter will be adsorbed and the gasoline driven out.

1f the contact is maintained long enough, the displacement of gasoline by water will become complete. Furthermore, this water displacement of adsorbed oils may be accelerated by working at a higher temperature. According to the present invention, it has been further discovered that when a gel having adsorbed in it a mixture of hydrocarbons, such as is obtained by bringing gel in contact with kerosene, is treated with Water, the lighter hydrocarbonsl are driven out more rapidly than the heavier fractions, particularly if the wat-er is cold. The products associated with the gel are, therefore, recovered in fractions, which is a very desirable method inasmuch as the most objectionable constituents in unrefined gasoline, which any process of refining seeks to remove, appear to consist largely o' highboiling hydrocarbons containing sulphur. (accordingly, the lighter and more valuable fractions of the adsorbed liquid may be displaced by agitation for a limited time with cold water and the liberated substance drawn ofi. The heavier fractions, including most of the objectionable sulphur compounds and other impurities, are liberated by agitation, repeatedly if necessary, with hot water. r'he oil recovered by cold water displacement is usually of about the same quality as the original unreined distillate and may be rerun. rlhe very much smaller fraction recovered by hot water agitation consists of relatively high-boiling constituents running high in sulphur and unsaturated hydrocarbons, and is suitable for `fuel oil. This fraction, regardless of its sulphur content, is unsuitable for burning as kerosene.

rlheproduct containing over 25% unsaturated hydrocarbons obtained from the pores of adsorbing material saturated by refining a petroleum product, is new. It is free from sulphuric acid and may run as high as 75% or more unsaturated hydrocarbons. Perhaps itmay best be defined as the product obtained from the pores of a porous material' having pores of a size to adsorb not less than 10% of its own Aweight of water at 30 C.

Maaate I 5 when exposed to water vapor at a partial ure 1) having the outlet pipe 108.l The adpressure of substantially 22 mm. of mercury, sorbing material to be activated is supplied which material has been used in ,refining a through the conduit 51. If necessary, water, petroleum product. This new product is or steam, or other gasmay be supplied to 5 particularly adapted for use as a flotation the interior of the activator through the inlet 70 l oil in the iotation process of recovering 110 which has communication with the cenmetals, because it has such a high percentage trally disposed tube 111 secured to the head of unsaturated hydrocarbons. 107. Usually, however, there is suiiicient he gel, or other porous material emwater in the adsorbing material supplied to 1o ployed, having been freed by water displacethe activator 52 sothat the steam necessary 75 ment of the `hydrocarbons and other constitfor distilling all the adsorbed substances is uents adsorbed from the liquid being refined, supplied from this source. It is the aim of is removed from the Wash Water, filtered, the arrangement to prevent ingress of air to aud the resulting gel Cake, Which 110W C011- the activator and have the adsorbed sub# tains practically nothing but water, is runl stances distilled out of the pores of the ad- 80 Into al1 activator Aand lts 'Water COIIteDt Iesorbing material, for the reason that if heat duced to the desired extent, usually 6 to 8%, as furnished. by the het gases alone is emlenderlllg the gel ready for re-use. ployedfor activating the adsorbing material,

Referring now to the drawings, the satuthere is danger of the deposition of carbona- 2o rated gel flows through the plpe 33 to a ceous and gummy materials within the pores 85 PM IDP 3.4 WlllCh-dlSChRIgeS 1110 Water Wash of the adsorbing material. This does not gllatOl 35 0f the Same Construction 11S the occur Where air is excluded from the acti- Otllel' agitatOI'Sl COld Water S Supplied t0 vator. The dried adsorbing material is disthis agitator through a pipe 35 so that the charged through the duct 112 into the intake gel S hOIOllghly IlllXed the Water OI' 0f the fan The 53 from the fan, 90 the PUI'PO Se 0f dllvng out the Substances discharges the gel or adsorbing material into adsorbed 111 the relilmg deSCIbed .abOVe a cyclone separator 55 wherein the gel settles This agltatOI dlSChaI'geS through a P1Pe-36 to the bottom and is discharged into a hopmtO a Separator 37 0f the same Construction per 56 from which it is fed by a sereween- 2S the other separators, n which the gel veyor 60 to the hopper 27 which discharges 95 settles to the bottomand gasoline or 'other' into agitator 1.33 thereby returning the gel petroleum` products liberated from the gel intothe rening eyele, If desired the gel are carried by the pipe 38 to the agitator 13 may be cooled and for this purpo the hopso that these products are again run through per 27 has its upper portion constructed with the refining process. The gel which settles `Cooling surfaces, The .vapor Aand air' sepa- 100 to the bottom of the separator 37 is 4car-y rated out by the cyclone separator may ried by pipe 39 to the pump 32 which d ls-l be discharged into the atmosphere, or, if it is charges into another agitator 41 supplied desired to recover any of the vapors or gases, with hot water by the pipe 42. This agitator they pass through a' pipe 57 to a condenser dISChargeS t e mixture mt@ another Sepa- 58. The condensate and gel not separated by4 105 rator 44. The fraction recovered by this hot the cyclone 55is drained through a pipe`59 water agitator, consisting of relatively hight0 a pump 60 which discharges through a boiling constituents, is. discharged through pipe 61 into the water wash agitator 4l. the pipe 46 and may be used for `fuel oil, or T0 prevent, any passage of vapors at the as a flotation oil. The gel .which settles to lower end of the cyclone separator 55, a 110 the bOOm 0f the .tllk 44 S CHJIIed by Pipe novel form of feeding device is employed. 47 to pump 48and discharged through pipe As shown in Figure 4, this comprises a 49 toa lter press 50 of any 4suitable .e011- plate 85 carried by an oscillating shaft 86 struction. In this press the surface Water disposed in a box 877 having a hopper bot- 50 is filtered out and the gel cakey discharged tom 456. The plate 85 is disposed hori- 115 through the pipe 51 to an activator 52. This zontally and is counterbalanced by the activator is illustrated in Figure 5. Brieiiy Weight 88. As shown vin Figure l, the plate Stated, it COIIlpI'lSeS a Cylindrical Shell 100 is disposed a slight distance below the lower with tubes 101 connecting the opposite heads end 0f the outlet of the cyclone separator M 102, T he Shen is provided with eireumfer- 55. The plate is escalated back and forth 12 entlal rings 103 supported by rolls 104 (F igin a horizontal plane in any suitable manure l) whereby the cylinder as a whole may ner,"'but the extent of oscillation is not sutlibe rotated. H ot gases are supplied through cient to open up the lower end of the cyclone the pipe 122 which has communication with at any time. For the purpose of oscillating n the chamber 106. This chamber in turn is the shaft 86 any suitable mechanism may be in communication with the interiorsof the employed. As shown, an arm 89 is secured tubes 101 so that the hot gases passvthrough to the upper end of the shaft and outside the tubes to the chamber 107 yat the opposite the box 87. ThisV arm is connected by a link end of the cylinder. This chamber is in to a crank pin 91 on the crank disk 92, 13o communication with a suction fan 109 (I1`ig-A the latter being carried by the armature shaft 93' of the motor 94. In operation, the continual oscillation of the plate 85 eifects a uniform feed of the adsorbing material into the hopper 56 but at no time permits passage of vapors.

If desired the discharge from the cyclone separator 55, in addition to being connected to the condenser 58 may have a return pipe 130 for conveying steam to a point adjacent the inlet of the fan 54, as shown at 113. In this manner the steam is used Aover and over again and a greater volume of gases is supplied to the fan so that the velocity in the pipe 58 is sutlicient to raise the adsorbing material therewith. It is to be understood that the pipes 53 and 130 are thoroughly lagged.

In refining some liquids it may happen, after the adsorbing material has made many cycles through the apparatus, that its absorbing eliciency will be decreased because of the deposition of carbonaceous or gummy materials within its pores. There this' is liable to occur an auxiliary activator may be employed to drive off these substances from the adsorbing material.

A As shown this auxiliary activator, in the form of the d rum 120, is disposed in the fur- I nace 121 which supplies hot gases through the pipe 122 to the main activator 52. Adsorbing material taken from the hopper 56 or other point may be carried through pipe 123 to the inlet end of the activator 120. This pipe may be supplied with a valve or damper 124 to control the flow of adsorbing material therein. At its dischargeend the auxiliary activator 120 has a blower 125 discharging through pipe 126 into a cyclone separator 127. The adsorbing material discharged through this pipe 126 is separated from the air and gases in the cyclone separater 127 and discharged into the cycle at any suitable point, as the worm conveyor 60. The gases from the top of the cyclone 127 are returned by pipe 128 to the activator 120 ata point adjacent the inlet of the blower 125. In this manner these gases are v used over and over to raise-the activated adsorbing material. A small quantity of the gases may be exhausted through pipe 128', and the loss made up by air supplied through pipe 123 at the inlet end of the activator. In this manner oxygen is obtained to burn the carbonaceous deposits in the pores of the material. It will be understood that the quantity of adsorbing material supplied to this auxiliary activator may be regulated by valve 124:. If desired, all of the adsorbing material from hopper 56 may be passed at intervals through the auxiliary activator 120.

It will be seen, therefore, that a-method is provided in which the porous ladsorbing material is used over and over in a closed cycle. Not only are the gums already present in the petroleum products removed, but

also the compounds capable of formingl gums, thereby obtaining a product whichl will permanently conform to the requirements as to doctor and gum tests, odor and color. Furthermore, the gums are removed without destroying the unsaturated hydrocarbons and the process is, therefore, par'- ticularly adapted for the refining of shale oils which may be as high as90% unsaturated.

It is noted that with the present method the use of sulphuric acid or other cheniicals is eliminated, also the losses resulting from the solvent and destructive action of sulphuric acid, particularly upon unsatu- -rated compounds in the product being relined. The process also eliminates any troublesome by-product, such as sludge acid. The reiining may be carried to any degree desired. The productl may be refined to such an extent that it will have a perinanently sweet odor, a permanently negative doctor test, a Water white color, even after indefinite exposure to direct sun light in the presence of air and moisture, and a sulphur content as low as 0.01%..

IV hen the present Vprocess is en'iployed to refine heavy or viscous oils or waxes, they will be maintained i-n fluid condition by the ap )lication of heat in any suitable manner.

' he term petroleum or petroleum products in the specification and claims are intended to include shale oils.

It is to be understood that the method constituting the present invention is not limited to the apparatus described, as the process may be carried out with other apparatus.

Having thus described the invention, what is claimed as new and desired to be secured by Letters Patent is:

-v 1. In the process of refining oils, the step consisting in. treating the oil with a solid absorbent material having pores of such size that it will adsorb water vapor to such an extent as to contain not less than about 10% of its own Aweight of water when in equilibrium With water v vapor at 30 C. and a partial pressure of substantially 22 mm. of l mercury. 1

'2. In the process of refining oils, the step consisting in treating the oil with' a hard porous adsorbent gel having pores of such size that itwill adsorb water vapor to such an extent as to contain not less than about- 10% of its own Weight of Watenwhen in equilibrium with water vapor at 30 C. and a partial pressure of 22mm. of mercury.

3. The process according to claim 1 Whereinthe adsorbing materials has pores of such size that it will adsorb water vapor to such an extent as to contain at least 21% of its own weight of water when in equilibrium with water vapor at 30o C. and a partial pressure of substantially 22 mm. of mercury.

. `not less than about 10% of such adsorbed water vapor when in equipartial pressure of 22 mm. of mercury.

porous silica gel having pores of such size` that it will adsorb water vapor to such .an extent as to contain not less than about 10% of its-own weight of waterwhen in equilibrium with water vapor at 30 C. and a p 5. In the process of refining oils, the step consisting in treating the oil with. a solid artificial adsorbent material having pores of such size that it will. adsorb water vapor to such an extent as to contain not less than about 10% of its own weight of water. when in equilibrium withwater va or at 30 C. and a partial pressure of su stantially" 22 mm. of mercury.

.6.I In the process of refining oils, the step consisting in treating the oil with a solid adsorbent material having pores of such size kthat it will adsorb water vapor to such an about 10%l extent as to contain not less than of its own weight of suchv adsorbed water vapor when in equilibrium with water vapor at 30 C. and a partial pressure of substantially 22 mm. of mercury.

7. In the process of refining oils, the step consisting in treating the oil with la solid, inorganic adsorbent material having pores of such'sizethat it will adsorb watervapor to such an extent yas to contain not less than abount 10% of its own-weight of such adsorbed water vapor when in equilibrium with water vapor at 30 C. and a partial pressure of substantially 22 mm. of mercury.l

8. In the process of refining oils, the step consisting inltreating the oil with a solid inorganic,artificial adsorbent material having pores'ofsuchsize that it will adsorb water vapor to such an extent as to` contain of its own weight to such an extent as to librium with water vapor at 30 C. and a partial pressure of substantially 22 mm. of mercury.

y 9. In the process of refining oils,y the step consisting Ain treating the oil with a solid inorganic, adsorbent material having pores of such size that it'will adsorb water vapor contain at least 21% of itsown weightof water when in equilibrium With Water vaporat 30 C. and a partiall pressure of substantially 22 mm. of mercury.

l0. The process of refining oils, which consists in treating the oil with a solid, inorganic adsorbent material having pores of such size that it will adsorb water vapor to `such an extent-as to contain not less than about 10% of its own weight of such ad-v sorbed water` vapor when in equilibrium with water vapor at 30 C. and a partial pressure of substantially 22 mm. of mercury,

separating theI adsorbent from the oil,l activating the adsorbent and returning the same to treat more oil, the adsorbent being circulated over and over in a closed path.

11. The process of refining oils which consists in treating the oil with a' hard, porous silica gel having v'pores of such size that it willl adsorb water vapor to such an extent as to contain not less than about 10% of its own weight of water when in equilibrium with water vapor at 30 C. and a partial pressure of 22 mm. of mercury, separating the adsorbent from the oil, activating the adsorbent and returning the same to treat more oil, the adsorbent being circulated over and over in a closed path.

In testimony whereof we hereunto affix our signatures.

WALTER ALBERT PATRICK. ERNEST BALDWIN MILLER. 

